Electrospinning technology has been widely recognized because of its ability to synthesize nanoscale fibers that are structurally similar to fibrillar structure of the natural extracellular matrix (ECM). Rendering the nanofiber surface to be biofunctional is critical for the successful application of the electrospinning technology in biomedical applications. Limitations in typical conjugation chemistry and physical adsorption procedures might be overcome by using polydopamine (pDA) coating inspired by adhesive proteins secreted by marine mussels. This perspective paper attempts to highlight an emerging area of the unique combination of electrospinning with pDA surface functionalization. The scientific progress and understandings of pDA coating chemistry mechanisms, coating processes and characterization with aids of nanoscale analytical techniques are reviewed and discussed. The intrinsic biomimetic morphological characteristics of the electrospun nanofibers united with the unique advantages of the pDA associated bio-functionalization have endowed a range of successful applications, especially in the interesting and important field of bioengineering.